Method of treating fibrous cellulosic materials to impart flame resistance thereto, composition therefor, and products thereof



MTFM Q i I A fi ta fet f sacs R OFFICE METHOD OF TREATING FIBROUS CELLU-LOSIC MATERIALS TO IMPART FLAME RESISTANCE THERETO, COMPOSITIONTHEREFOR, AND PRODUCTS THEREOF Joseph W. Creely, East Bound Brook, N.J), as-

Signor to American Cyanamid Company, New York,'N. Y, a corporation ofMaine No Drawing. Application February 1, 1950,

' S erialNo. 141,852

This invention relates to methods of imparting flame resistance tocellulosic material, more par-" ticularly natural orregenerated'cellulosejor mixtures thereof; and specifically to textilescomprising fibers of such cellulosicmaterials. The invention furtherrelates to the" compositions used in such methods and to the.flame-resistant cellulosic products thereof.

In the past, various "compounds and compositions have been used orsuggested for use as agents for treating fibrous cellulosic materialsand other normally flammable organic materials in order to' render'them'resistant to flame; A e s or trea ments or. m art n am rre st: ance toordinarily flammable organic materials may be classified as (1)temporary (2) semidurable and (3). permanentv or. durable. Thisclassification is based on the durability. of the treatment in providingcontinued resistance of the treated textile or. other material to flameduring use.

The durable treatments heretofore used orv suggested have been of threegeneral types: (1) urea phosphate (2) double bath precipitation,'(3)m'et'allic oxide-chlorinated 'body. Oneof the main, objections tothe urea-phosphate typeof treatment has been its tendering effect on thecellulosic material whereby its tensile strength is reducedconsiderably. The double bath precipitation and the metallicoxide-chlorinated body types of treatment generally yield cellulosictextiles having a harsh or stiff hand so that the treated textile has alimited field of utility. The above disadvantages have been overcome byprocesses for impartingfiame resistance to cellulosic textile materialsdescribed in the copend ing applications of Anne MacMillan Loukomsky,Roy H. Kienle, and Theodore'R. Cooke, Serial No. 76,644, filed February15, 1949, now U. S. Patent No. 2,520,103, and Serial No. 64,416, filedDecember 9, 1948, now U. S.'Patent No. 2,519,388. The first of theseapplications describes impregnation of fibrous cellulosic materials witha composition containing specified proportions of (1') a finely dividedoxide'of antimony, (2) a thermally unstable halogen-containingthermoplastic substance, (3) a water-soluble salt of an oxygencontainingacid of phosphorus in which'phosphorus has a valence of 5, and (4)either cyanamide, dicyandiamide or mixtures thereof, while the latterapplication discloses a similar use of a composition containingspecified proportions of 1) a finely divided oxide of tin, titanium,antimony or bismuth, (2) a thermally unstable halogen-containingthermoplastic substance, (3) a water-soluble salt of'anoxygen-contiaining acid 17 Claims. (Cl. 1 1'7--103) of phosphorus inwhich phosphorus has a valence of 5, and (4) urea, biuret, ammoniumcyanate or ammonium dicyanimide.

Later it was found that byjudicious selection of the particular,ingredient falling within class (3) of the above identified applicationsthe necessity for including a member of class (4) in compositions for.imparting flame-resistance to cellulose textiles might be eliminated.The three component'compositions and their use for impartingflame-resistance to textiles are described and claimed in my copending"application with Theodore F. C'ooke,Srial No. 141,851, filed Febmay 1',1950, entitled"Permanent Flameproofing commune-Kim r cedure? It is anobjectof the present invention to provide an additional method for,imparting fia-meresistance to cellulosic textile materials which avoidsthe disadvantages of the urea phosphate, double bath precipitation ormetallic oxide-chlorinated body types of treatment. g

It is another object of the present invention to impart flame-resistanceto cellulosic textile materials.

It is still another object of the present invention to provide apermanently flame-resistant cellulosic textile material which has animproved hand over that of flame-resistant cellulosic textile materialsgiven a double bath precipitation treatment or a metallicoxide-chlorinated body type of treatment.

Another object of the present invention is to so treat cellulosictextile materials that they be come permanently flame-resistant withoutexcessive tendering.

The above and other objects are attained by impregnating a cellulosictextile material with ingredients comprising (1) a finely divided oxideof tin, ti um, antimony, bismuth, or mixtures thereof, (2) a ing atleast 20% by weight of combined halogen and capable of rupturing underheat at carbonhalogen bonds, the ingredients (1) and (2) together beingdesignated hereinafter as (A), and i (B) a water-soluble, metal-free,nitrogencontaining salt of an amino phosphoric acid having 5 an aminonitrogen atom attached directly to a ermoplasticfiu'b'stancemontafinphosphorus atom which salt has 'a' melting point 2 of less than 200 C.The impregnant may be applied to the cellulosic textile material as asingle aqueous liquid composition containing the ingredients of both (A)and (B) or as two separately applied aqueous liquid compositions, onecontaining the ingredients of (A) and the other containing theingredient (B).

The invention will be described in greater detail in conjunction withthe following specific examples in which proportions are given in partsby weight unless otherwise noted. The examples are merely illustrative,and it is not intended that the scope of the invention be limited to thdetails therein set forth.

ONE BATH APPLICATIONS Example 1 A bath is prepared containing '75 partsof phosphoric acid product #1 (see below), 6.2 parts of antimony oxide(SbzOa), 5.6 parts of polyvinyl 4 A bath (b) containing 5.6 parts ofpolyvinyl chloride, 6.2 parts of antimony oxide (613203) and 88.2 partsof water is prepared and used to impregnate the padded cloth to give awet pick-up 5 of about 93%. The treated cloth is then dried in an ovenwith forced air circulation to give a dry add-on of about 10.9%.

After one wash a char length of 3 inches and no afterglow are observed.After five washes the cloth shows a char length of 3% inches and anafter-glow of seconds.

Example 8 is repeated using different impregnating bath with thefollowing results:

Ex. Formulation pH 9 98% #1, 2% HMTA 1 10 50% #1, urea, 2% HMTA..-"

Char Length in Afterglow in Bath (a) Bath (b) Inches secs.

Wet Dry Wet Dry Pickup Addmn Pickup Adchm 1 wash 5 washes 1 wash 5washes Per cent Per cent Per cent Per cent 123 20.9 94 11 3% 3% none 6117 16 99 11. 6 3% 3% none 5 105 13 100 11. 7 3 3% none 3 101 13 99 11.6 3 5 none 6 111 10.8 98 11.5 3% 4 none 6 121 16. 6 93 10.9 3 4% none 5125 11.2 07 11.3 4 5 none 3 117 20. 3 92 10.8 3% 4% none 5 121 15. 3 9310. 9 4 4 none 4 119 21. 92 10.8 3% 3% none 5 121 12 90 10.5 3% 3% none5 125 19. 7 93 10.9 3% 3% none 6 106 8. 7 106 12. 4 4 l 4% none 2 1108.0 104 12. 2 4 5% none 3 124 18 94 11 3% 5 none 3 118 21 96 11. 2 4 4none 5 I r 1 HMTA=hexamethylenetetramino.

chloride, and 13.2 parts of water. This solution, which has a pH ofabout 6.8, is padded on bleached, unmercerized 80 x 80 cotton" cloth togive a wet pick-up of about 125%. The padded cloth is air dried, curedfor 15 minutes at 160 C., rinsed and again dried to give a dry add-on ofabout After one wash a char length of 3 inches is obtained by thevertical flame test, and the cloth has no after-glow. After five washesthe char length is 3 inches and the after-glow, 7 secs. Details of boththe washing and flame testing procedures used in this and all followingexamples are given below.

Example 1 is repeated using diiferent impregnating baths with thefollowing results:

Wherever the percentages of ingredients in the formulations appearing inthe above tables do not total 100%, the balance is water.

Similar results are obtained when the antimony oxide of the examples isreplaced wholly or in part by oxides of bismuth, titanium or tin or bymixtures of two or more of the oxides.

Preparation of phosphoric acid products 1. 2 mols 85% H3PO4 and 6 molsurea are mixed 5 in a glass tray and heated in an oven for one hour at160 C. A 97.7% yield of a glassy substance is obtained. This isdissolved in sufficient water to make about a 59% solution.

2. 0.5 mol (as H4P2O7) polyphosphoric acid containing 32-50% meta,47-60% pyro, 3-8% ortho Bath Per One Wash Five Washes Per E Cent Heb DryChar Aftcr- Char After- Formulation pH u Add- Length, Glow, Length,Glow, p on Inches Secs. Inches Secs.

2-.. 37.5% #1, 2% HMTAJ 18.8% urea, 6.2% SbqOg, 5.6% PVC 7. 3 123 26 3%none 4 5 3... #3, 6.2% 512103, 56% PVC 6. 2 26 3% none 4 5 4... 37.5%#3, 2% IIMTA, 18.8% urea, 6.2% 513203, 5.6% PVC 6. 8 124 31 3 5 none 3%6 5 37.5% #4, 2% HMTA, 18.8% urea, 6.2% SbzOa, 5.6% PVC 6. 8 124 81 3%none 3% 6 6... 37.5% 18.8 urea, 6.2% Sbg03, 5.6% PVC 6.9 127 3O 3% none3% 7 7... 37.5% #8, 2% llMlA, 18.8% urea, 6.2% SbzOs, 5.6% PVC 2.4 12530 4 none 3% 7 l HMTA hexamethylenctetremine. 1 PV C polyvinyl chloride.

TWO BATH APPLICATIONS Example 8 Bleached, unmercerized 80 x 80 cottoncloth is padded with a bath (a) of phosphoric acid product #1 having apH of about 6.7 to a wet pick-up of about 123%. The cloth is dried in anoven with forced air circulation, cured for 15 minutes at C., rinsed andagain dried to give a dry add-on of about 22.6%.

SIEUSS 5. tray and heated for one hour at 160C. An about 84.7 yield of aglassy product is obtained. A 50% solution of this product in Water ismade. 4. 2 mols urea and 2 mols monoguanidine phosphate are mixed in aglass-tray and heated for one hour at 160 C." An about 89.4% yield of aglassy product is obtained. This is dissolved in an equal weight ofwater. i

5. 2 mols urea and 2 mols monoguanidine phosphate are mixed in a glasstrayjand heated for 30 minutes at 160 C. in an oven. One-third molhexamethylenetetramine is stirred in,- and the mixture is heated anadditional 20 minutes. The foaming melt is cooled and weighed. Yield:about 95.4% white solid. A 50% solution of this in water is prepared. Iv

- 6. 2-mols (as H4P2O1) polyphosphoric acid and 2 mols urea are mixedtogether-and heatedat 160 C. in an oven.. A white foam forms whichsolidifies on cooling. Yield: about 87%.

7. '1 mol monoguanidine phosphate, 0.5 mol dicyandiamide and about -6mols water are heated one hour at 160 C. A white foam results An about100% yield on the weight of solid reactants is obtained. The product isdissolved in an equal Weight of hot water. I v

8. 1 mol HaPO (85%), 0.5 mol dicyandiamide and about 6 mols water areheated one hour at 160 C.- A white gummy substance results in about a94% yield.

"FLAME TESTING PROCEDURE Flame tests on the impregnated cotton fabricsof the examples are made following a procedure which is in general thatgiven in ASTM Tentative Specifications Designation: D626-41T issued1941. Samples 2 /2 inches x 10 inches are cut with the long dimensionparallel to the warp. The sample of fabric to be tested is suspendedvertically in a shield by means of a clamp at the top and bottomthereof. A Bunsen burner previously regulated to a luminous flame 1inches high is placed under the suspended sample so that the end of thesample extends A inch into the flame. The flame isheld under thesamplefor 12 seconds and thenextinguished. The total length of char in inchesis measured by the tear length produced with a tearing weight equal toapproximately 10 of the tearing strength of the unburned fabric.

WASHING PROCEDURE The washings referred to in the preceding examples areefiected in small oscillating machines. A one pound load is used foreach wash, and the fabrics are washed for 15 minutes intervals using 12liters of 0.5% neutral soap solution at 65-75 C. They are spun andrinsed for from 3-5 minutes in lukewarm water and then spun and rinsedfurther by hand.

The present inventionis not.limited to the particular polyvinyl chlorideof the examples and the thermoplastic substance may be any thermoplasticmaterial containing at least and preferablyatleast 40%, by weight ofcombined halogen which is capable of rupturing under heat atcarbon-halogen bonds. Some examples of such thermoplastic materials arethe polyvinyl bromides, the polyvinylidene chlorides, the polyvinylidenebromides, copolymers of vinyl halide and vinylidene halides as, forexample, of vinyl chloride and vinylidene chloride, copolymers of vinylhalides and acrylic esters as, for example, of vinyl chloride andmethyl, ethyl, propyl, butyl or the like acrylates, halogenatedparaffins, halogenated diphenyls as pentachloand the cations of'whichcontain nitrogen and no metal. Ammonium salts and guanido type saltssuch as the guanidine, guanylurea and biguanide salts of the followingamino phosphoric 'acids are-representative of those which are suitablefor use:

. 0% on 7 V s Monoaminodiphosphoric XQ h I O. OH Diaminodiphosphoric PI, o \NH, PN'Hz 0 OH Triaminodipliosphoric PO(OH) P 0(08)Diaminotetraphosphorie PO(OH) Tetraminotetraphosphorlc The monoandpoly-salts may be used. I prefer, in general, the ammonium and guanidinesalts and more particularly, salts containing a cationic ammonium orguam'dine group for each phosphorus atom in the acid.

The amino phosphoric acid salts may conveniently be prepared by meltingtogether (1) urea or dicyandiamide and (2) phosphoric acid, apolyphosphoric acid or a guanido type salt of phosphoric acid or of apolyphosphoric acid. When the free acid is reacted with urea ordicyandiamide, the ammonium salt of the amino phosphoric acid isobtained. When the urea or dicyandiamide is reacted with the guanidotype salt of a phosphoric acid, the corresponding guanido type salt suchas the guanidine, biguanide, guanylurea, etc., salt of the aminophosphoric acid is obtained. The invention is not, however, in any waylimited to any particular method of preparing the amino phosphoric acidsalts.

The cellulosic textile material may be impregnated with the ingredientsof the present process in one or more steps or stages as illustrated bythe specific examples. It may be impregnated with a dispersioncontaining all of the necessary ingredients within the range ofproportions specified below or it may be given a twobath treatment. Ifthe latter, the textile must be impregnated first with (B), the aqueoussolution containing the water-soluble, metal-free, nitrogen-containingsalt of an amino phosphoric acid having an amino nitrogen atom attacheddirectly to a phosphorus atom, and then after drying with (A), thedispersion containing the metallic oxide and the thermally unstablethermoplastic substance.

Regardless of the method of impregnation of the fibrous cellulosictextile material it is important that the ingredients of (A) and (B) beemployed in a weight ratio of 1 part of the former to from 0.2-8 partsof the latter just as it is important that ingredients (1) and (2) of(A) be employed in a weight ratio of 1 part of the former to from 0.6-20parts of the latter.

The total amount of the ingredients of (A) and (B) with which cellulosictextile materials are impregnated according to the present process mustbe sufficient to impart flame-resistance to the materials after heatingthem within the range of 135-200 C. and thereafter washing to remove anyresidual water-soluble substances. The total amount of the ingredientsof (A) and (B) with which the cellulosic material is impregnated is socontrolled that the finished flame-resistant textile contains from about10 %-50% by weight or, if the hand of the treated material is relativelyunimportant, to as high as about 75% by weight, based on the dry weightof the untreated textile, of wash-fast impregnant. During the heattreatment at 135-200 C. a substantial loss of solids takes place whichmay be as much as of the total weight of the phosphate with which thecellulosic material was initially impregnated. In order to obtain a,finished textile containing from 10%-50%, or in those cases wheredesired up to 65%-75%, by weight based on the dry weight of theuntreated textile, of wash-fast impregnant, the amount of solids in thetextile as initially impregnated should be sufiiciently hight to allowfor this weight loss of solids during the heat treating and washingsteps.

I prefer to employ an aqueous dispersion of the necessary ingredientsfor treating fibrous cellulosic textile materials in accordance with myinvention. The amount of solids in such a dispersion may be varied asdescribed but they will usually constitute from about 40% to about byWeight of the dispersion.

The present invention applies to cellulosic materials of the classconsisting of natural celluloses, regenerated celluloses and mixturesthereof and including primarily cotton and viscose rayon.

The textile treating compositions of this invention may be modified byincorporating therein various modifying agents which aid in furtherimproving the flame-resistant characteristics of the treated cellulosicmaterial or which facilitate the technique of application. For instance,the compositions may also contain minor amounts (e. g., from 1% to 30%weight of the total solids content) of such glow retardants as theglow-retarding borates, phosphates, pyrophosphates, etc., e. g., zincborate, zinc phosphate, zincammonium phosphate, stannic phosphate,phenyl diamido phosphate, melamine pyrophosphate, etc. Agents which havea buffering effect on the composition after being applied to the fabricor other textile, e. g., calcium carbonate, magnesium oxide, urea,hexamethylene tetramine and other polyalkylene polyamines boiling aboveabout 200 C., the amount of said polyamines not exceeding about 7% byweight of ingredient (B), etc., may be incorporated into the treatingcompositions as desired or as con ditions may require. It is oftenadvantageous to add an agent such as urea which will convert anyaminophosphate which may have been hydrolyzed back to theaminophosphate.

Bath (B) in a two-bath process should be adjusted to a pH (glasselectrode pH) within the range of from about 3 to about 7 if it is notinitially within that pH range. Preferably the pH of the aqueouscomposition containing ingredient (B) is between about 4 and 6.

The present invention is applicable to the production of a wide varietyof flame-resistant cellulosic materials, e. g., wearing apparel of allkinds, especially childrens clothes and clothing used by the armedforces, curtains, draperies, sheeting, furniture coverings, linings forelectric blankets, net fabrics, non-woven fabrics, chenilles, etc.,which are made of cellulosic textile materials.

The terms flame resistance and flame-rcsistant as used herein and in theappended claims with reference to cellulosic textile materials are usedgenerically to include within their meanings treated cellulosic textilematerials,

4 which, after ignition, will continue to burn at a r l l l 9 erly fall:within; the specific-classification ,of fire-resistant cellulosictextile materials.

The terms textile and textile material as used generically herein and inthe appended claims include within their meanings filaments, fibers,rovings, slivers,- threads, syarns, twisted yarns, etc.,.as'suchi 'orin. woven, felted or otherwise formed fabrics, sheets, cloths and thelike.

Iclaim: I .1 A.

A method orimparting flame-resistance to a cellulosic textile materialof the class consisting of natural celluloses, regenerated cellulosesand mixtures thereof, which comprises impregnating said material witharr-association of an aqueous liquid.composition containing ingredientscomprising (1) .a finely divided oxide of'a metal of the groupconsisting of antimony, bismuth, tin and titanium and (2) athermoplastic substance containing at least 20% by weight of combinedhalogen and capable of rupturing under heat at carbon-halogen bonds, theingredients of (l) and (2) which together are designated hereinafter as(A) being employed in a weight ratio of 1 part of the former to from0.6-20 parts of the latter, and of an aqueous liquid compositioncontaining an ingredient comprising (B) a water-soluble, metal-free,nitrogencontaining salt of an amino phosphoric acid having an aminonitrogen atom attached directly to a phosphorus atom, which salt has amelting point of less than 200 C., the ingredients of (A) and (B) beingemployed in a weight ratio of 1 part of the former to from 0.2-8 partsof the latter, the aqueous composition containing the ingredient (B)having a pH of from about 3 to about 7; heating the impregnated materialat a temperature within the range of about 135-200 C'.; and washing theresulting material to remove any residual water-soluble substancestherefrom, the total amount of the ingredients of (A) and (B) with whichthe cellulosic textile material initially is impregnated being such thatthe finished flame-resistant textile contains from about to about '7 5%by weight, based on the dry weight of the untreated textile, ofwash-fast impregnant.

2. A method as in claim 1 wherein the cellulosic textile material iscotton.

3. A method as in claim 1 wherein the cellulosic textile material isviscose rayon.

4. A method as in claim 1 wherein the metal oxide is antimony oxide.

5. A method of imparting flame-resistance to a textile comprising fibersof a cellulosic material of the class consisting of natural celluloses,regenerated celluloses and mixtures thereof which comprises impregnatingsaid textile with an aqueous dispersion having a pH within the range of3-7 and comprising (1) a finely divided oxide of a metal of the groupconsisting of antimony, bismuth, tin and titanium, (2) a thermoplasticsubstance containing at least by Weight of combined halogen and capableof rupturing under heat at carbon-halogen bonds, the ingredients of (1)and (2) which together are designated hereinafter as (A) being employedin a weight ratio of 1 part of the former to from 06-20 parts of thelatter, and (B) a water-soluble, metal-free, nitrogen-containing salt ofan amino phosphoric acid having an amino nitrogen atom attached directlyto a phosphorus atom, which salt has a melting point of less than 200C., the ingredients of (A) and (B) being employed in a weight ratio of 1part of the former to from 0.2-8 parts of the latter; heating theimpregnated textile at a temperature within the range of about 135- 200C,; and washing the resulting textile to remove any residualwater-soluble substances therefrom, the total amount of the ingredientsof (A) and (B) with which the textile initially is impregnatedbeingsuchthat the finished flameresistant textile contains from about 10% toabout 75% by weight, based on the dry weight of theuntreated textile, ofwashv-fast impregnant.

.tfipA-method as in claim 5-wherein ingredient (2). is a vinyl chloridepolymerization product.

7. A method as in claim 5 wherein ingredient B) is the amino phosphoricacid salt obtained by reaction of urea'with phosphoric acids.

. 8. A method as in claim 5 wherein ingredient (B) is theaminophosphoric acid salt obtained by reaction of urea withpyrophosphoric acid.

9. A method as in claim 5 wherein ingredient (B) is the amino phosphoricacid salt obtained by reaction of urea with monoguanidine phosphate.

10. A method as in claim 5 wherein ingredient (B) is the aminophosphoric acid salt obtained by reaction of dicyandiamide withphosphoric acid.

11. A method as in claim 5 wherein ingredient (B) is the aminophosphoric acid salt obtained by the reaction of dicyandiamide withmonoguanidine phosphate.

12. A method as in claim 5 wherein the aqueous dispersion contains asmall amount, not exceeding about 7% by weight of the ingredient (B), ofa polyalkylene polyamine having a boiling point substantially above 200C.

13. A method of imparting flame-resistance to a textile comprisingfibers of a cellulosic material of the class consisting of naturalcelluloses, regenerated celluloses and mixtures thereof which comprisesimpregnating said textile with an aqueous solution having a pH withinthe range of 3-7 and containing (B) a water-soluble, metal-free,nitrogen-containing salt of an amino phosphoric acid having an aminonitrogen atom attached directly to a phosphorus atom, which salt has amelting point of less than 200 C.; heating the impregnated textile at atemperature within the range of 200 C.; washing the resulting textile toremove any residual water-soluble substances therefrom; impregnating theheated and washed textile with ingredients comprising (1) a finelydivided oxide of a metal selected from the group consisting of antimony,bismuth, tin and titanium and (2) a thermoplastic substance containingat least 20% by weight of combined halogen and capable of rupturingunder heat at carbon-halogen bonds, the ingredients of (1) and (2) whichtogether are designated hereinafter as (A) being employed in a weightratio of 1 part of the former to from 0.620 parts of the latter, theingredients of (A) and (B) being employed in a weight ratio of 1 part ofthe former to from 0.2-8 parts of the latter; and heating theimpregnated material at a temperature within the range of about 135 C.to 200 C., the total amount of the ingredients of (A) and (B) with whichthe said textile is impregnated being such that the finishedflame-resistant textile contains from about 10% to about 75% by weight,based on the dry weight of the untreated textile, of wash-fastimpregnant.

14. A flame-resistant cellulosic textile material obtained in accordancewith the method of claim 1.

15. A flame-resistant cellulosic textile material obtained in accordancewith the method of claim 5.

gether are designated hereinafter as (A) being employed in a weightratio of 1 part of the former to from 0.6-20 parts of the latter andbeing dispersed in water containing (B) a water- 15 2,413,163 soluble,metal-free, nitrogen-containing selling. 4 2,75

atom, which salt has a melting point of less than 200 (2., theingredients of (A) and (B) being employed in a weight ratio of 1 part ofthe former to from 0.2-8 parts of the latter.

JOSEPH W. CREELY.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date Bacon Dec. 24, 1946 Ford et a1Sept. 27, 1949

1. A METHOD OF IMPARTING FLAME-RESISTANCE TO A CELLULOSIC TEXTILEMATERIAL OF THE CLASS CONSISTING A NATURAL CELLULOSES, REGENERATEDCELLULOSES AND MIXTURES THEREOF, WHICH COMPRISES IMPREGNATING SAIDMATERIAL WITH AN ASSOCIATION INGREDIAQUEOUS LIQUID COMPOSITIONCONTAINING INGREDIENTS COMPRISING (1) A FINELY DIVIDED OXIDE OF A METALOF THE GROUP CONSISTING OF ANTIMONY, BISMUTH, TIN AND TITANIUM AND (2) ATHERMOPLASTIC SUBSTANCE CONTAINING AT LEAST 20% BY WEIGHT OF COMBINEDHALOGEN AND CAPABLE OF RUPTURING UNDER HEAT AT CARBON-HALOGEN BONDS, THEINGREDIENTS OF (1) AND (2) WHICH TOGETHER ARE DESIGNATED HEREINAFTER AS(A) BEING EMPLOYED IN A WEIGHT RATIO OF 1 PART OF THE FORMER TO FROM0.6-20 PARTS OF THE LATTER, AND OF AN AQUEOUS LIQUID COMPOSITIONCONTAINING AN INGREDIENT COMPRISING (B) A WATER-SOLUBLE, METAL-FREE,NITROGENCONTAINING SALT OF AN AMINO PHOSPHORIC ACID HAVING AN AMINONITROGEN ATOM ATTACHED DIRECTLY TO A PHOSPHORUS ATOM, WHICH SALT HAS AMELTING POINT OF LESS THAN 200* C., THE INGREDIENTS OF (A) AND O(B)BEING EMPOLOYED IN A WEIGHT RATIO OF 1 PART OF THE FORMER TO FROM 0.2-8PARTS OF THE LATTER, THE AQUEOUS COMPOSITION CONTAINING THE INGREDIENT(B) HAVING A PH OF FROM ABOUT 3 TO ABOUT 7; HEATING THE IMPREGNATEDMATERIAL TO REMOVE ANY RETURE WITHIN THE RANGE OF ABOUT 135*-200* C.;AND WASHING THE RESULTING MATERIAL TO REMOVE ANY RESIDUAL WATER-SOLUBLESUBSTANCES THEREFROM, THE TOTAL AMOUNT OF THE INGREDIENTS OF (A) AND (B)WITH WHICH THE CELLULOSIC TEXTILE MATERIAL INITIALLY IS IMPREGNATEDBEING SUCH THAT THE FINISHED FLAME-RESISTANT TEXTILE CONTAINS FROM ABOUT10% TO ABOUT 75% BY WEIGHT, BASED ON THE DRY WEIGHT OF THE UNTREATEDTEXTILE, OF WASH-FAST IMPREGNANT.